CN1689711B - Method for surface hydrophilicity of fluid assembly and system - Google Patents

Method for surface hydrophilicity of fluid assembly and system Download PDF

Info

Publication number
CN1689711B
CN1689711B CN200510066910.0A CN200510066910A CN1689711B CN 1689711 B CN1689711 B CN 1689711B CN 200510066910 A CN200510066910 A CN 200510066910A CN 1689711 B CN1689711 B CN 1689711B
Authority
CN
China
Prior art keywords
fluid
hydrophilic polymer
liquid
assembly
fluid assembly
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN200510066910.0A
Other languages
Chinese (zh)
Other versions
CN1689711A (en
Inventor
M·J·P·莱娜
L·维斯
D·沃克尔
W·蔡勒
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
F Hoffmann La Roche AG
Original Assignee
F Hoffmann La Roche AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by F Hoffmann La Roche AG filed Critical F Hoffmann La Roche AG
Publication of CN1689711A publication Critical patent/CN1689711A/en
Application granted granted Critical
Publication of CN1689711B publication Critical patent/CN1689711B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/04—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a surface receptive to ink or other liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
    • B01L3/502707—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by the manufacture of the container or its components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/483—Physical analysis of biological material
    • G01N33/487—Physical analysis of biological material of liquid biological material
    • G01N33/49—Blood
    • G01N33/4915—Blood using flow cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2200/00—Solutions for specific problems relating to chemical or physical laboratory apparatus
    • B01L2200/12—Specific details about manufacturing devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L2300/00—Additional constructional details
    • B01L2300/16—Surface properties and coatings
    • B01L2300/161—Control and use of surface tension forces, e.g. hydrophobic, hydrophilic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2201/00—Polymeric substrate or laminate
    • B05D2201/02—Polymeric substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/14—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by electrical means
    • B05D3/141—Plasma treatment
    • B05D3/142—Pretreatment
    • B05D3/144—Pretreatment of polymeric substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
    • B05D7/222—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes of pipes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
    • B05D7/227—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes of containers, cans or the like
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T436/00—Chemistry: analytical and immunological testing
    • Y10T436/20—Oxygen containing
    • Y10T436/207497—Molecular oxygen
    • Y10T436/208339—Fuel/air mixture or exhaust gas analysis

Abstract

The invention describes a method for manufacturing a thin film of a hydrophilic polymer on the inner surface of a constituting component for fluid. The inner surface of the constituting component for fluid is subjected to a physicochemical treatment and more particularly a plasma treatment, and thence, the inner surface is brought into contact with a hydrophilic polymer solution and thereafter the polymer solution is substituted with a medium of gas by such a method that the inner surface is first kept wet by a portion of the polymer solution and finally the thin film of the hydrophilic polymer is made to remain on the inner surface of the component for fluid by removing the solvent in the final. The hydrophilic polymer used in this case has higher surface wettability to an aqueous solution than the surface wettability on the inner surface of the constituting component itself for the fluid.

Description

By the method for the surface hydrophilic of fluid assembly and system
Technical field
The present invention relates to produce the durable film of hydrophilic polymer on the inner surface of fluid assembly, particularly improve its surface nature, for example it is for the method for the wettability of the aqueous solution.
The invention still further relates to the fluid assembly that has this hydrophilic polymer film on surface therein.
The invention still further relates to the fluid system for delivery of liquid that at least comprises a this fluid assembly, and for the production of the method for this fluid system.
Finally, the present invention relates at least one physics for measuring liquid, particularly body fluid or the analytical system of chemical parameters, it has at least one fluid system for measuring the sensing element of this parameter and being made up of fluid assembly, has hydrophilic polymer film on the inner surface of this fluid assembly.This analytical system can be especially for diagnosing relevant parameter from humoral determination.
Background technology
For measuring the physics of liquid or the modern analysis system of chemical parameters has complicated fluid system conventionally, this fluid system must ensure that underproof liquid is transferred and arrives sensing element substantially uninterruptedly, and ensures that fluid sample is transported to leave sensing element after measuring described parameter.
This analytical system is by especially for clinical diagnostics, and wherein they are especially used to blood gaseous analysis or other measurement of the sample that exists with liquid form.This system is used to for example measure the oxygen of blood or overall hemoglobin, oxyhemoglobin, carbonyl haemoglobin or the methamoglobin of partial pressure of carbon dioxide, for example whole blood of hemoglobin parameters or hemolytic blood, hematocrite value and the pH value of whole blood, or such as lithium, sodium, potassium, magnesium, calcium or chlorine root plasma or special for example glucose, urea, kreatinin or the lactate concentration in physiological fluid of metabolin.The analytical system of this complexity has different sensing elements conventionally, and to measure corresponding parameter, they are used to much mensuration.This class sensing element is for example for the electrochemistry of mensurated gas composition value, pH value, ion value and metabolin value or optical pickocff or for the optical measuring device of Measuring hemoglobin value.US Patent No. 3,874,850 (Sorensen etc.) have described the analytical system of this class for blood analysis.This system has several sensing elements, and they are used to measure the pH value of blood sample, dividing potential drop and the content of hemoglobin of oxygen and carbon dioxide.These sensing elements connect by complicated fluid system, described fluid system is made up of various fluid assemblies, for example pipe, storage tank and waste canister, pump or valve, in this system, sample is transported to analytical system by means of syringe or capillary from patient.
Except this type systematic, the system that can use nearby patient is also known, and wherein by means of pipe-line system, fluid sample is directly transferred to analytical system from patient.This type systematic is described in for example U.S. 6,080,583 (von Bahr).
Except the fluid subsystem for delivery of sample liquids and/or quality control medium; many analytical systems also comprise other fluid subsystem conventionally, to for example carry liquid or even gas calibration medium and/or washing or cleansing medium from storage container to sensing element and from there to waste canister.The conveying of various media is by pump and valve control along path, and described path is partly different.
Using complicated fluid system, is the Omni S analytical system from Roche Diagnostics GmbH for another example of the system of measuring several diagnosis relevant parameters from sample liquids.Comprise blood gas, electrolyte, total hemoglobin, CO oximetry, metabolin and bilirubin with the parameter area of this system of modular form setting, and it only requires little sample volume, be therefore particularly suitable for Neonatal Ward.
Fig. 1 has shown the sketch of the fluid system of Omni S system.In this case, the connecting line between single fluid assembly represents that fluid connects, and according to predetermined application, it can be designed to pipe or pipeline.The roundlet showing in these fluids connect represents to can be used for controlling the valve that liquid is carried.They are designed to press from both sides valve conventionally.The rod vertical with fluid line connector represents coupling element, and it can be used for making fluid assembly to contact with each other.The sample path of the fluid line connector express liquid sample drawing with triplet from supply opening 8 to sensing module 1a to 1d.Region 1a represents sensing module to each of 1d, and it can be made up of several sensing elements.Therefore, sensing module 1a can comprise for measuring for example element of lactate, urea or glucose of metabolin, sensing module 1b can comprise the ion-selective electrode for measuring calcium, potassium, sodium or chlorine root, sensing module 1c can comprise for measuring oxygen and carbon dioxide dividing potential drop and for measuring the blood gas sensor of pH value, and sensing module 1d can comprise the sensing element for Measuring hemoglobin and haemoglobin dervative.Underproof sample is introduced the fluid system of analytical system via supply opening 8, sample is transported to each sensing module 1a to 1d from supply opening 8 along sample path, and sample is also halved during carrying whereby.This function completes by means of the valve that is arranged in sample path.Also can introduce with on path identical with the sample path of sample itself and be transported to sensing module by supply opening for the liquid of quality control object.The process that liquid is carried along sample path is monitored by means of physical sample sensor 7, and it provides the flat information of dress water-filling of system except other function.The sample of introducing therein valve is distributed between 1c by the inherent sensing module 1a of again integrated transit system 2.Be present in liquid container 6 for liquid clean or correction object, it is connected to the remainder of fluid system by pipe or pipeline, and can be fed in fluid system with control mode by means of valve.These solution and sample solution are carried by means of the peristaltic pump 3 that is connected to fluid system via valve.The sample consuming and liquid thereby help vavuum pump 5 and are transported to collection container 9 via fluid system from sensing module, finally arrive waste canister 4.
The instrument in these class modern times is application sample and liquid very in a small amount conventionally, they conventionally in fluid system by decile again.Depend on number and the type of determined parameter, the sample volume of requirement can be for example 50 to 120 microlitres.But, need special means, not contaminated to ensure such small sample volume to be transported to the sensing element of analytical system.Pollution can be for example by remaining in the residue of the previous sample in fluid system or the residue of tester, correction or cleaning medium are caused.Pollute for fear of this class, can for example between the single mensuration of measured value, insert washing and drying steps.
In the case of the sensing element for mensurated gas composition, for example electrochemistry or optics gas sensor, and in the optical measuring system situation of for example Measuring hemoglobin, owing to comprising bubble in fluid system, particularly in sensing element region, comprise bubble, therefore still have the danger that produces measure error.Therefore in the time utilizing Electro-chemical Gas Sensor to measure the gas measured object in liquid, in the time that sample or quality control or calibration reagent are not filled the liquid-conveyor zones of sensing element completely, or when existing bubble for example when air bubble in this region, sample determination or proofreading and correct or quality control in may go wrong.When there is inhomogeneous inner surface in fluid system, when this inner surface has different wetabilitys to liquid, especially can form bubble.In fluid system, there is the position of sudden change in the wetability of the inner surface of each fluid assembly, especially can form or bubbles attached.For example, in the time that surface is made up of the different materials being adjacent to each other, be exactly this situation.But the fluid system of many analytical systems is made up of many single fluid assemblies, they are made up of the different materials of the abutment surface with different wetabilitys.In addition, many fluid assemblies of this alanysis system are made of plastic, and it has low hydrophily and hydrophobic character.This class frosting is by liquid, aqueous wetting poor performance and especially have and form or the tendency of bubbles attached.
WO02/070590 (Faure etc.) has described the method for the hydrophiling on hydrophobic substrates surface, wherein the hydrophilic polymer film having existed is applied on base material.Because the handling property of the prefabricated very thin hydrophilic polymer film of this class is poor, therefore as disclosed in WO02/070590, applying this class performed thin film is very difficult and complicated technically, may, to the inner and therefore mechanically stress application of surface of for example pipe of very unattainable fluid assembly, be therefore infeasible economically hardly.
The U.S. 6,432,510 (Kim etc.) have described the method for improvement of surface wettability, and wherein the surface of base substrate is first by physico-chemical process roughening.Utilize subsequently physical method, for example, from vapour deposition coating material, the thin layer of the coated substance with good wetability is applied on the surface of these roughenings.At US6, in 432,510 method, key point is, the roughening of the matrix material carrying out above must even be maintained after coated substance is applied in, to improve wetability.But the surperficial fluid assembly with this class roughening is not suitable for diagnostic analysis system, because physiological fluid contacts and causes risk of pollution greatly to improve with this class roughened surface, and therefore need obviously more additional washing and cleaning step.Particularly, the porous of test(ing) liquid and high molecular component, especially, the in the situation that of blood, the danger of this class surface attachment is improved greatly.
US5,212,000 (Rose etc.) have described by introducing the special polymer solution with thixotropic property, produce the painting method of polymeric layer on the inner side of thin flow element.As the result of these special thixotropic properties, at least some polymer solution is stayed on the inner side of film as coating protection.But, use these class methods to be only limited to special application, and can only use special thixotropy coating solution to implement.As the result of these thixotropic properties, especially in the system that therein liquid passes through via the inner chamber of flow element in some cases under very high pressure, due to the impact of these pressure and/or volume flow, exist coated substance again to liquefy and depart from surperficial danger.
BP0379156 (Fan) has described painting method, wherein first polyisocyanate solution is applied to the surface of medical device, particularly catheter, (optionally) this solution is dry, the solution of the polymer that comprises hydroxy-acid group with after-applied another kind.In this two steps or multistep process, conventionally need many processing steps, relate to several reagent solutions and chemical reaction step, to obtain the coating needing.But, for simple and economical as far as possible coating technique, advantageously need the least possible processing step and reaction solution.
US4,752,426 (Cho) have described the method for surface hydrophilic, wherein first utilize Low Temperature Plasma Treating to produce from the teeth outwards chemically reactive group or free radical.Subsequently monomer solution is applied to this surface.Monomer and lip-deep chemically reactive group or free radical chemically reactive, finally utilize glycerol polymerization to form from the teeth outwards coating.The shortcoming of this method is that processing step and condition must be mated each other completely.For example, must select by plasma processing parameter, make as far as possible only to form from the teeth outwards these and can also in glycerol polymerization subsequently, be used as chemically reactive group or the free radical of polymerization core.
Summary of the invention
Therefore, the object of this invention is to provide the method for improvement of the surface wettability of fluid assembly inner surface, the method has been avoided the shortcoming of prior art.
Object of the present invention provides in particular and can implement and can be by the method for fluid assembly inner surface hydrophiling in simple and the most most economical mode, it is stable that this hydrophiling acts in long-term use, and is resistance to physics or chemical stress.
Another object of the present invention is to provide fluid assembly and system, wherein in long-term use, can be reduced in the danger of adhering to or form bubble on these fluid assembly inner surfaces.
In addition, the object of this invention is to provide at least one physics for measuring liquid or the analytical system of chemical parameters, wherein in long-term use, can reduce the danger that sample liquids pollutes, particularly owing to adhering to or forming the danger of the pollution that bubble or other material cause on these fluid assembly inner surfaces.
The method that hydrophilic polymer film is provided on fluid assembly inner surface by providing in the present invention has reached these objects, in the methods of the invention, first convection cell module inner is carried out physical chemistry processing, subsequently fluid assembly inner surface is contacted with hydrophilic polymer solution, then replace in such a way the solution of hydrophilic polymer with gaseous medium, first the inner surface of fluid assembly is kept by the hydrophilic polymer solution-wet of part, by removing desolventizing, the film of hydrophilic polymer is retained on the inner surface of fluid assembly with last.According to the present invention, the surface wettability for the aqueous solution that the hydrophilic polymer of use has is higher than the surface wettability there is no fluid module inner under hydrophilic polymer film.
The present invention is by providing fluid assembly and system to reach these objects, on the inner surface of described fluid assembly and system, directly there is the film of hydrophilic polymer, and do not exist other intermediate layer, described film to use especially said method of the present invention to produce.
The present invention reaches these objects by the method that is provided for producing hydrophilic polymer film on the inner surface of this class fluid system.
The present invention is by being provided for measuring at least one physics of liquid or the analytical system of chemical parameters has reached these objects, this analytical system comprises at least one for measuring at least one physics of liquid or the sensing element of chemical parameters and the fluid system for liquid is transported to sensing element and/or transfers out from sensing element, described fluid system comprises one or more fluid assemblies, on the inner surface of described fluid assembly, directly there is the film of hydrophilic polymer, and there is not other intermediate layer, described film produces by the above-mentioned method of the present invention especially.
For the present invention is described, below some term is explained:
In the application's scope, fluid assembly refers to any assembly that is suitable for reception, conveying or dispense liquid substantially.Especially, within the scope of the present invention, assembly is considered to fluid assembly, because it has specific stereochemical structure, be designed to mode specific and that limit receive, conveying or dispense liquid.Fluid assembly is often used as the assembly of fluid system, and is used in this connection carry liquid in this system.This class fluid assembly can be realized various functions, and especially, they can be used as such as bottle of liquid container, reagent packaging, separator or waste canister, for delivery of liquid, for example pipe, pipeline, passage or the region of carrying the sensing element of liquid, as valve or control element, for example pinch valve, mixing valve, pressure valve or valve three-way pipe, as liquid absorbing device, for example pin, pipe or the inlet forming especially, be used for being connected to such as joint of various assemblies, docking elastomer, T-or Y-joint, cruciform joint, angled connector or plug-in connector, or for sealing function, for example potted component.In order to realize its function, pipe is for example made up of elastomeric material, and can carry for the liquid limiting especially, for example, use the folder valve for regulating and controlling.Especially, they can be used for analytical system, the specific conveying for sample liquids to sensing element, and as the assembly that can be assembled simply, for liquid is transported away, for example, enter waste canister.In contrast, rigid pipe is conventionally by having some physical property for example transparency, air impermeability, thermal conductivity or can making by cleaned material, and conventionally can be used as fluid assembly, for wherein not carrying by means of the liquid in the folder valve field that regulate.Connection Element, for example inserted sleeve, T-or gamma-form joint, cruciform joint, angled connector or plug-in connector, be typically used as fluid assembly, to connect between the liquid-conveyor zones at for example pipe, pipeline and sensing element of other fluid assembly.Docking elastomer is the particular of connected system, its permission so that the mode of user operation the single component of fluid system is inserted frequently or is disconnected.This class connected system can for example be used to reagent packaging, to they are connected in once-through operation to fluid system.This class connected system can be used for easily dismantling and changing the single component of fluid system.The particular form of liquid absorbing device is so-called charging aperture.These are used to receive outside liquid container, for example capillary, syringe or connect skirt.This class charging aperture is used in the fluid connection that produces sealing between external sample container and diagnostic analysis system, makes by this way, and sample liquids can be injected or suck analytical system safely.For example bottle of liquid container or reagent packaging are used to store and liquid is provided, for example, proofread and correct liquid and clean and regulator solution.Solution can for example be removed from these liquid containers by means of suction.For the connection between two stiff fluid assemblies, use especially the potted component connecting for fluid.Fluid assembly can also have the more complicated device for delivery of liquid, for example transit system.In the application's scope, fluid assembly or the liquid-conveyor zones of sensing element.These are understood to be the region of the sensing element that may directly contact with underproof liquid, and therefore have the inner surface in the application's meaning.It can be for example the liquid carrying in sensing element for and discharge sample channel, or can also be a part for the sensor itself that directly contacts with liquid, the gas-permeable membrane of for example Electro-chemical Gas Sensor.In photo measure method situation, for example, in hemoglobinometry situation, a part of holding the sensing element of analyzed liquid volume in measuring described measured value is also considered to fluid assembly.Fluid assembly is made up of the material of the particular/special requirement that meets fluid assembly conventionally.For example, pipe is made up of silicon rubber or soft polyvinyl chloride conventionally, pipeline is by polyvinyl chloride, polyamide or acrylonitrile-butadiene copolymer form, transit system Merlon, polymethyl methacrylate, acrylonitrile-butadiene copolymer or styrene-methacrylic-butadiene copolymer are made, connector polypropylene, Merlon or polyamide are made, docking elastomer acrylonitrile-butadiene rubber, silicon rubber or Viton are made, charging aperture is made with silicon rubber or polyether-ether-ketone, bottle and liquid container are made with polyethylene, with potted component natural rubber, silicon rubber or Viton are made.
Within the scope of the application, fluid system is considered to the combination of several fluid assemblies, and described fluid assembly links together by this way, and liquid can be transferred between these fluid assemblies.Especially, this class fluid system is suitable for reception, conveying or dispense liquid.By means of by various fluid assemblies in conjunction with form fluid system, the function of single fluid assembly can be combined, make the fluid system obtaining can also carry out complicated fluid function.Therefore, for example, can in the path of regulation, carry the fluid system of the liquid volume of regulation to form by means of the applicable combination of pipe, valve and pump.This class fluid system can comprise any amount of fluid assembly, and can have the complexity of any degree.Owing to thering is stereochemical structure, can carry out the single component of the function of several fluid assemblies, also can be considered to fluid system.This class complex assemblies can for example be manufactured in Shooting Technique, and this technique allows complicated especially transit system to manufacture single component.Fluid system is especially used to analytical system, and wherein liquid-the conveyor zones of sensing element is also considered to the assembly of fluid system.
In the application's scope, analytical system is considered to any system, it has at least one for measuring at least one physics of liquid or the sensing element of chemical parameters, and fluid system for liquid is transported to sensing element or transfers out from sensing element.Analytical system can have several fluid subsystems, and they are independent of each other or connected to one another, and several sensing unit or module.For example, analytical system can have the fluid subsystem for delivery of sample or quality control liquid, with the fluid subsystem for delivery of liquid and gas calibration medium and/or washing or cleaning medium, they are for example connected and are formed total fluid system by valve.
In the application's meaning, sensing element is considered to all can be used for the measuring physics of liquid or the devices of chemical parameters.These can be in particular and the sensor that is occurred directly to contact by test specimen, or for example utilize the optical measurement of transmission or scattered light indirectly to measure the sensor-based system of physics or chemical parameters.The sensor of front type can be for example electrochemistry or optical pickocff, for measuring gas value, pH value, ion value or the metabolin value of blood sample.The sensor-based system of the second type can be for example the optical measuring device of the Hemoglobin Value for measuring blood sample.The sensor of front type occurs directly to contact with underproof liquid, makes the liquid-conveyor zones of this class sensing element play the effect of fluid assembly.In the sensor-based system of the second type, be used to the region of the described system of carrying liquid, the region of the described system that especially comprises analyzed liquid volume in measuring described measured value can be considered to fluid assembly with regard to its function.For example, in optical measuring system situation, they can be spectroscopic assay path or absorption cell in fluid system.
In the application's meaning, sensing module is considered to the combination of several sensing elements conventionally.This class sensing module can have several sensing elements especially in common housing, and they have common fluid subsystem.This class sensing module can for example be designed to box or sensor array, and they are used on the basis of single injected sampling sample and substantially side by side measure much physics or chemical parameters.This class sensing module can for example have such fluid system, the fluid conveying space of its branch that has single fluid intake, opening or comprise one or more passages, and single fluid outlet.The homogeneous turbulence body conveying space contact together of several sensing elements, therefore this fluid conveying space plays common sample channel in this sensing module.
In the application's meaning, the inner surface of fluid assembly or fluid system is considered to the surface contacting with the liquid being transferred, and it is three-dimensional form, and fluid assembly is used to liquid with this form and carries.These are for example inwalls of pipe, pipeline or passage, and it may contact with the liquid that flows through them.But in this connection, the whole inner surface of fluid assembly not necessarily must touch described liquid.
In the application's meaning, hydrophilic polymer is understood to be such polymer, and it is made up of same type or dissimilar monomer structure portion, and has hydrophily performance.The polymer chain of this base polymer is hydrophilic, or at least has hydrophilic chain sequence.This class hydrophilic polymer has the chemical group that glassware for drinking water is had to high affinity, for example hydroxyl or ether group.The example of hydrophilic polymer is some polyethers, for example some polyethylene glycol or some polypropylene glycol, some glycan, for example some dextran or some polyalcohols, for example some polyvinyl alcohol.Especially, some polyethers-polyurethane copolymer also can be used as hydrophilic polymer.Major advantage of the present invention is, this hydrophilic polymer must only not produced on coating surface, but described hydrophilic polymer chain can be applied on described surface with the form of solution.This makes the present invention distinguish over especially the hydrophilic coating that by polymerization precursor, especially utilizes plasma polymerization or glycerol polymerization to produce from the teeth outwards, because the inventive method is used the hydrophilic polymer of polymerization, this hydrophilic polymer is made up of non-covalent cross-linked polymer chain substantially, does not therefore need complicated polymerization procedure.That the repeatability of manufacturing thin layer depends on many factors, and may therefore can not always be guaranteed by means of another shortcoming of carrying out the coating processes of polymerization by precursor from the teeth outwards.According to the present invention, use this class hydrophilic polymer can directly and simply produce hydrophilic coating, and do not need additional chemical reaction step.For this purpose, in order to obtain durable hydrophilic coating, polymer chain must not be cross-linked to each other.The polymer of the application of the invention, even in the situation that there is no covalent cross-linking, they also can form durable hydrophilic polymer film.Therefore, can particularly preferably use the hydrophilic polymer being formed by non-covalent crosslinked polymer chain.This is particularly advantageous, because use the hydrophilic polymer of polymerization, compared with polymerization formation film, is more not time-consuming with precursor on substrate surface.
In the application's meaning, hydrophilic polymer is the polymer molecule of polymerization in particular, and especially compared with long-chain polymer molecule, it does not have covalent cross-linking together, and therefore still can be dissolved in applicable solvent with suitable amount.In this case, non-covalently crosslinked be understood to mean single polymer chain and there is no with covalent bond and link together.But, be applied on the surface of wanting coated and after forming thin polymer film at non-covalent crosslinked polymer of the present invention, between single polymer chain and/or can form subsequently the unspecific covalent bonding of slight extent between single polymer chain and surface, or form this bonding as the result of for example storage process of process subsequently.But, can be for example optional for production and/or the creative performance of thin polymer film at nonspecific this class bonding forming between single polymer chain or between polymer chain and surface as the result of Cement Composite Treated by Plasma.Therefore, they can and only want on coated surface the chemical bond between individual molecule and/or surface from precursor is produced to differentiate significantly at thin polymer film, for this situation, the chemical bond of these formation is necessary with conclusive for the production of thin polymer film forming and performance.
In the application's meaning, film is understood to be the substantially continuous and uniform layer of material on base material, it is coated in the form of dissolving on the surface of wanting coated by material that will be coated especially, then removes desolventizing or solvent mixture and produces to form film.
In the application's meaning, term surface wettability or wetability are used as measuring of surperficial hydrophily or hydrophobic properties.Can easily conventionally be there is high-hydrophilic by liquid, aqueous wetting surface and material.Angle of wetting or contact angle are defined as the measurement means of wetability, it is understood to be so a kind of angle, this angle is the angle with respect to the surface of solids at the tangent line of the profile of three phase point place drop, and represents the measurement means of the character that a kind of surface or interface soaked mutually by another.Angle of wetting is less, and wetability is higher, and surface more has hydrophily.Especially in the time that angle of wetting is less than 90 °, surface can be by water-wet.
In the application's meaning, all substances and mixture of substances, it is liquid and has the water content that is greater than 50 % by weight, is considered to liquid, aqueous or solution under standard conditions.They can be solution or even or heterogeneous mixture, for example dispersion, emulsion or suspended substance.Especially, they can be sample liquids, particularly body fluid or fluid therefrom, for example blood, blood plasma, serum, urine, cerebrospinal fluid, tears, dialysate or such liquid.Liquid, aqueous can also be salting liquid, cushioning liquid, calibration solution, reference solution, quality control solution, washing or clean solution, reagent solution or the solution that comprises standardization analyte concentration, so-called standard sample.
In the application's meaning, organic solvent and solvent mixture are to have the solvent and the solvent mixture that are less than 50 % by weight water content.
Method and apparatus of the present invention can provide fluid system, and it allows the wettability of the inner surface of single fluid assembly to match each other.This can be reduced in the danger of adhering to or form bubble between the long-term operating period on the inner surface of fluid system.According to the present invention, reach this object by means of there is identical hydrophilic polymer film on the inner surface at fluid assembly or fluid system.Hydrophilic polymer this class film on fluid assembly inner surface can be produced especially simply and economically by the inventive method.In addition, the hydrophilic polymer film of producing by the inventive method is firmly adhered to the inner surface of fluid assembly, and very resistance to physics or chemical stress, and therefore they are particularly useful for diagnositc analyser.
The inventive method is characterised in that following steps sequence:
1. first, the inner surface of fluid assembly is stood to physical chemistry processing.
In this process, the part of fluid assembly inner surface that is provided at least subsequently hydrophilic polymer film is processed.To this, during this processing, assembly exists using the form being present in fluid system as fluid assembly later, is not indispensable.In certain embodiments, and especially in assembly situation flexibility or flexible, inner surface can improve by changed element shapes before processing the accessibility of this processing.Therefore, for example, can first section of a pipe be turned over from inside to outside, make inner surface outside, subsequently present outside surface is processed, and finally again this section of pipe turned over from inside to outside, make pretreated surface again inside, by this way its inner surface is processed.In another embodiment, the outside of section of a pipe can be first through processing.Subsequently this section of pipe overturn outwardly by inner, make the surface of the processing of this section of pipe become its inner surface.In other embodiments, first process on the surface of the discrete component of convection cell assembly, and subsequently these element assemblings are formed to fluid assembly.When in complicated fluid assembly, inner surface for this class process be not can arrive or be not easy arrival time, this may be especially favourable.The tolerance of the film of the cohesive of the film that the pretreatment of inner surface has improved hydrophilic polymer especially to inner surface and coating to physics or chemical stress.Physical stress can be understood to be especially in long-time with aqueous specimen liquid and particularly body fluid for example blood, blood plasma, serum or urine repeat contact.The physical stress of this class in long-time, may As time goes on reduce the layer thickness of hydrophilic polymer film, or film may depart from from fluid assembly inner surface completely or partially.Chemical stress may be especially to contact with for example rodent cleaning solution of rodent chemical reagent.Before applying hydrophilic polymer film, process inner surface, can use physico-chemical process to carry out, preferably carry out by means of Cement Composite Treated by Plasma.But, can carry out film described in pretreatment with other physico-chemical process in essence, for example Ion Beam Treatment or by for example sodium naphthalene solution-treated of oxidation material.This class surface treatment method is known, and be for example described in " by means of the surface modification of the polytetrafluoroethylene film of chemical etching, plasma and Ion Beam Treatment ", KimS., Journal of Applied PolymerScience, 2000, the 77th volume, 1913-1920 page, or WO94/06485 (Chatelier etc.).Surface-treated chemical method is not preferably those methods that wherein apply for example adhesive phase of additional intermediate layer.On the contrary, in this application, cause surperficial reactivity to improve and substantially do not change surface chemical composition for surface-treated physico-chemical process, be considered to preferred method.In preferred embodiments, before producing hydrophilic polymer film, the inner surface of fluid assembly is processed by means of Cement Composite Treated by Plasma.Before coated polymer solution, obtained the combination between inner surface and thin polymer film with Cement Composite Treated by Plasma inner surface, such combination is enough good for film physics or chemical stress to height endurability.This class physics Cement Composite Treated by Plasma allows to save and uses for surface-treated toxic chemical.With gaseous plasma pretreatment inner surface cause surface even modification, its extend into surfacing compared with low depth.In this class, for the plasma method of surface preparation, the gaseous plasma that comprises ionizing particle is by discharge generation, or by under the pressure reducing in gas atmosphere line electromagnetic field produce.This gaseous plasma can be used for producing from the teeth outwards reactive region, and therefore at least temporarily improves its reactivity, and thin polymer film is improved to the cohesive of inner surface and its tolerance to physics or chemical stress.
2. in next processing step, the inner surface of fluid assembly is contacted with the solution of hydrophilic polymer.
The inner surface of fluid assembly can utilize all methods well known by persons skilled in the art with this contact of hydrophilic polymer solution, for example use solution rinsing or fill fluid assembly, fluid assembly is immersed in solution, or by solution spray on inner surface.In this method, can on the whole inner surface of fluid assembly, provide hydrophilic polymer film, or only provide in some part of inner surface.Especially, these subregions can be after in fluid system those regions of contact liq.In preferred embodiments, hydrophilic polymer solution is used to this processing step, this hydrophilic polymer dissolves in organic solvent and solvent mixture, and water insoluble solution substantially, and is insoluble to especially sample liquids and moisture clean or calibration solution.Especially, use this class hydrophilic polymer fluid assembly inner surface for good and all and soundly to be applied in effective mode, and do not use additional chemical reaction step.Use the hydrophilic polymer of water insoluble solution substantially can reduce in fact the dissolving of film in liquid, aqueous, and therefore this class film is very durable in this class medium, and is therefore particularly useful for diagnostic analysis system.In preferred embodiments, polyethers-polyurethane copolymer is used as hydrophilic polymer.This class polyethers-polyurethane copolymer is described in for example United States Patent (USP) 5,728,762 (Reich etc.) and the U.S. 5,932,200 (Reich etc.).Preferred polyethers-the polyurethane copolymer of this class is the block copolymer with hydrophilic region and water repellent region.As the result of these amphiphilic performances, polymer can dissolve preferably in some organic solvent and solvent mixture, they itself form the hydrogel with hydrophilic surface performance after removing organic solvent or solvent mixture on the other hand, its water insoluble in fact solution, and be therefore particularly suitable for coating of the present invention.Particularly suitable polyethers-the polyurethane copolymer of this class can be for example from Cardio Tech International, Inc., and Wobum, MA, the U.S. obtains.
According to the present invention, produce film by the film of directly manufacturing hydrophilic polymer on the inner surface of fluid assembly, and do not use other intermediate layer.As surface-treated result of the present invention, this surface of modification by this way in first processing step, make between inner surface and thin polymer film, to have enough bonding forces, and film has the high tolerance to physics or chemical stress.Therefore,, before applying hydrophilic polymer film, there is no need to carry out from the teeth outwards the coating of for example adhesive phase of complicated additional intermediate layer.
3. in next processing step, with gaseous medium alternative hydrophilic polymer solution by this way, the first inner surface of fluid assembly is kept by a part of hydrophilic polymer solution-wet.
In this process, any excessive polymer solution that may exist is removed by importing gas volume, and a certain amount of polymer solution is remained on the surface of wanting coated.Excessive polymer solution can be removed on one's own initiative or passively.Especially, this can be undertaken by introducing by this way gaseous medium, and fluid assembly is rinsed by this gaseous medium, and therefore makes excessive polymer solution be replaced by this medium.In other embodiments, this can be by removing fluid assembly from hydrophilic polymer solution, and allow excessive polymer solution to flow away from the surface of coated fluid assembly, and by around gaseous medium particularly air replace polymer solution to complete.In addition, remain on amount and/or the concentration of lip-deep polymer solution by adjusting, can limit especially and regulate the thickness that is applied to surperficial hydrophilic polymer film.
4. in last processing step, on the inner surface of fluid assembly, produced the film of hydrophilic polymer by removing desolventizing or solvent mixture.
In this last processing step, the solvent or the solvent mixture that are retained in lip-deep polymer solution are removed, and last hydrophilic polymer film is retained on this surface.Removing of solvent or solvent mixture must at least proceed to such degree, makes the film of the mechanically stable that retains from the teeth outwards hydrophilic polymer.In this case, solvent or solvent mixture can be removed passively, for example, by slow evaporation in outside atmosphere, or accelerated on one's own initiative, for example, by applying vacuum or low pressure, by using gas bleed surface, or accelerate evaporation by improving temperature.
In some embodiment of described method, can first in the surface of single component or the region of fluid assembly and particularly its liquid-conveyor zones, provide the film of hydrophilic polymer, and assemble subsequently these elements to form fluid assembly.
Another aspect of the present invention relates to fluid assembly, it is characterized in that, hydrophilic polymer film is directly present on the inner surface of fluid assembly, and there is no other intermediate layer.Especially, the present invention relates to have the fluid assembly of hydrophilic polymer film on inner surface, wherein hydrophilic polymer film produces by the one of the inventive method as above.
On inner surface, exist hydrophilic polymer film to change the physical surface character of fluid assembly.Especially, this type coating can improve the ability that these surfaces are soaked by the aqueous solution, and therefore reduces the danger that comprises or form bubble.On the inner surface of fluid assembly, exist another effect of this quasi-copolymer film to be, in these surfaces, the nanometer of any existence can be compensated by produce film on these faces significantly to the roughness of micrometer range.In the time that this class fluid assembly is used to diagnostic analysis system, this is particularly advantageous, because this alanysis system has the caused risk of pollution of the material owing to retaining in the mensuration above or cleaning step of raising conventionally.This class material, especially from porous or the macromolecular substances of body fluid, for example protein, is more prone to deposit on surf zone coarse or that be very difficult to arrive.According to the present invention, on these faces, exist the stabilizing films of hydrophilic polymer to reduce the danger that this class is polluted in long-term use.
In preferred embodiments, the inner surface of fluid assembly is made up of plastics.In the application's meaning, and according to the definition of the standard committee of " Plastics in the DIN ", plastics are understood to be " material that its necessary component is made up of macromolecular organic compound, this macromolecular organic compound is formed or formed by modified natural product by synthetic ".Under many circumstances, they can for example be melted and molding under certain condition under heat or pressure.The performance of rubber and chemical fibre is also included within the middle of plastics them.Plastics are particularly suitable as the material of flow element, because its performance can change in every way, and therefore can be optimally adjusted to adapt to the function that must complete in fluid system, for example, accomplish this point by changing its elasticity.Many plastics can be with the whole bag of tricks molding well known by persons skilled in the art, for example injection moulding or deep-draw method, and therefore the shape of fluid assembly can be adjusted to be adapted to its function in fluid system especially.Inter alia, used the material of following plastics as fluid assembly: polyamide, Merlon, polypropylene, polyethylene, polymethyl methacrylate, polyvinyl chloride, polyether-ether-ketone, acrylonitrile-butadiene copolymer, styrene-methacrylic-butadiene copolymer, natural rubber, silicon rubber, acrylonitrile-butadiene rubber or Viton.
In preferred embodiments, on the inner surface of these assemblies the thickness of hydrophilic polymer film between 0.01 to 50 micron, preferably between 0.01 to 10 micron, particularly preferably between 0.01 to 5 micron.On fluid assembly, apply thin thin polymer film, can meet the surface nature of convection cell assembly and the especially requirement to its wetability or surface texture on the one hand, the production of this class film can be cost-saving especially on the other hand, and therefore make the use of hydrophilic polymer more economical.
Another aspect of the present invention relates to the fluid system for delivery of liquid, it is made up of several fluid assemblies, these fluid assemblies are connected by this way, and liquid can be transferred between these fluid assemblies, and comprise at least one fluid assembly of the present invention.In the fluid system being formed by several fluid assemblies, in the position of single fluid assembly contact, there is sudden change in the wettability of the inner surface of each fluid assembly wherein, for example, owing to having different surfacings especially, may form or bubbles attached, or may contaminant deposition matter.According to the present invention, by single fluid assembly on inner surface, there is hydrophilic polymer film, the preferably film of identical hydrophilic polymer, can address the above problem.On the inner surface of single fluid assembly, there is identical hydrophilic polymer film, the physical characteristic of these assemblies and especially its wettability are mated, therefore prevented in fact pollution.
According to the present invention, the film of hydrophilic polymer must not be present on the whole inner surface of fluid system.Under many circumstances, just enough in the time that this class film is only present on some region of fluid system or the inner surface of some fluid assembly or these surfaces partly.If fluid system is used to analytical system, and be used to especially diagnostic analysis system, fluid system with lower area in hydrophilic polymer film is provided, the sample bringing device from the transport path of corresponding sensing element upstream starts, or hydrophilic polymer film is provided in the liquid-conveyor zones of sensing element itself, normally enough for the described measured value of accurate and error free mensuration.Other region of the fluid system of hydrophilic polymer film should be preferably provided, it is the region that is arranged in the same fluid system in sensing element upstream, but it is not used in conveying sample liquids, but for example feed correction or cleaning medium, and conventionally flow into the transport path of the sample liquids of sensing element upstream.The region of the fluid system in sensing element downstream, for example, must not have hydrophilic polymer film to the conveyance conduit of waste canister, because the bubble in these regions or pollution do not have adverse effect to the mensuration of measured value.
Another aspect of the present invention relates to the method for producing this class fluid system, and this fluid system has hydrophilic polymer film on surface therein at least in part.
In preferred embodiments, this class fluid system is produced by first producing hydrophilic polymer film on the inner surface of the single fluid assembly of assembled formation fluid system or the less sub-assembly of this class fluid assembly subsequently.Apply therein whole fluid system or its large parts economically also in unaccommodated situation, or because the single subregion of for example system is not accessibility or is not easy to arrive, therefore this class is coated in technically when being infeasible or very difficult, can use especially said method.These can be for example subregion or the very narrow liquid delivery path of valve fluid system below.But in order still to produce hydrophilic polymer film in this class region of fluid system, the single fluid assembly that its inner surface should have hydrophilic polymer film is provided this class film first individually, and assembling forms fluid system subsequently.By this way, can also the part in simple mode as system provide hydrophilic polymer film, in the system of assembling, such part applies and can not reach for this class, or be very difficult to reach.
In a further preferred embodiment, by the inner surface of the single fluid assembly of the ground pretreatment of physical chemistry first, subsequently these assembly assemblings are formed to fluid system, and on such assembling fluid system, carry out other processing step of the present invention and produce this class fluid system.This process can be especially for such situation, wherein the physical chemistry pretreatment of whole fluid system or its large parts is not economically viable, or because technical reason is impossible or very difficult, for example, because the single fraction of system is not accessibility for this class pretreatment or be difficult to arrive.In some preprocess method, particularly the in the situation that of Cement Composite Treated by Plasma, occur sometimes such problem, i.e. pretreated effect is limited in the region of the easy arrival of fluid system, and can not be pretreated or be very difficult to pretreated in the region that is difficult to arrive of fluid system.In order to overcome this problem, provide a kind of so method at this, the method has solved the problems referred to above by means of following content: do not make whole fluid system or its large parts stand this class pretreatment, but first only single fluid assembly or its part are carried out to pretreatment, therefore can more easily carry out pretreatment.Therefore, one section of the discrete component of for example valve or long section pipe can, by pretreatment individually, be assembled subsequently.Other step of producing hydrophilic polymer film on the inner surface of fluid system is not crucial conventionally, and can in the system of assembling, carry out.
In above-mentioned embodiment, film can also be produced for the described processing step of single fluid assembly by enforcement on the less sub-assembly of several these class fluid assemblies.
For example, before starting the inventive method, fluid assembly, for example pipe or elbow, can be assembled into little sub-assembly, and carry out the subsequent step for produce hydrophilic polymer film on inner surface as common little sub-assembly.
Another aspect of the present invention relates at least one physics for measuring liquid or the analytical system of chemical parameters, it comprises that at least one is for measuring at least one physics of liquid or the sensing element of chemical parameters, and for liquid being transported to sensing element and/or being transported away the fluid system of the present invention of liquid from sensing element.
In this alanysis system, can use the embodiment of all previously described fluid systems of the present invention.On this alanysis system principle, can be used to analyze all types of liquid, and particularly preferably be used for analyzing liquid, aqueous.In preferred embodiments, this alanysis system is used to analyze physiological fluid, for example blood, blood plasma, serum, urine, myelencephalon liquid, tears fluid, or liquid bio sample, for example cell suspension, cell conditioned medium liquid, cell extract, histolysis product or similar liquid.They are by particularly preferably for analyzing blood, serum, blood plasma or urine.
In preferred embodiments, the film of hydrophilic polymer is also present on the liquid-conveyor zones of analytical system or the inner surface of one or more sensing elements.Liquid-the conveyor zones of these sensing elements directly contacts with analyzed liquid.The film that has hydrophilic polymer in these regions is particularly advantageous, because it can reduce the danger due to the measured value distortion that exists bubble or polluter to cause in sensing element.In particularly preferred embodiments, by the liquid-conveyor zones of sensing element and have the film of identical hydrophilic polymer on the adjacent part of remaining fluid system, can further reduce this class danger.
In a further preferred embodiment, analytical system comprises several sensing elements, to measure different physics and/or the chemical parameters of the liquid that is generally used for many mensuration.But, except can be repeatedly with nonexpondable sensing element, can also use can only expendable sensing element.In this case, each element links together by the fluid assembly that also can be in direct contact with one another conventionally.In this respect, various sensing elements can also be combined into sensing module, and they have shared fluid subsystem.
Detailed description of the invention
Embodiment 1: as for example outer shell passage with preparing hydrophilic polymer film on the pretreated flow element of plasma
The shell channel of sensing element, for example oxygen electrode has been described as an example of fluid assembly hereinafter.This shells passage is equivalent in fact the liquid-conveyor zones of sensing element, and it directly contacts with liquid, and the sample channel that provides in sensing element and remove liquid is be provided.Fig. 2 has shown the example of the section of the sensitive zones of this class sensing element, and this sensing element uses the lambda sensor of Clark type as an example, and it is for the OMNI analytical system of for example Roche diagnostics.These sensing elements (10) comprise for delivery of with sample or the shell channel (12) of sampling, and actual sensor (11), it has inner electrolyte space and is arranged on electrode wherein.Gas-permeable and in fact ion-and liquid-impermeable plastic foil (13) between inner electrolyte space and sample channel, it separates inner electrolyte space with sample channel.In the situation that showing, the wall of the housing of sensing element (15) and shell channel (12) is made up of for example methyl-propyl acid methyl esters-BS of transparent plastic.For pretreatment shell channel before the hydrogel coating actual, housing (15) is fixed on support plate, and be placed in the plasma apparatus from the V15-G type of Plasmafinish company, and under 2.45GHz, use helium plasma treatment a few minutes according to the explanation of manufacturer.Shown in the situation that, the opening in the housing that plasma can cover via the opening of shell channel (12) both sides and via later tunicle (13) enters the inner side of shell channel.After completing Cement Composite Treated by Plasma, in about 5-60 minute, the housing of plasma-processing is removed from support plate, and be fixed in housings support thing.In this housings support thing, the fluid pipeline that provides and discharge liquid is connected to the two ends of shell channel (12).By means of being present in the compressible seal (14) on housing (15) or being present in the sealing on fluid pipeline, by pressure, bindiny mechanism seals fluid pipeline.Via fluid pipeline and therefore via the solution of shell channel (12) suction hydrophilic polymer X1, continue a few minutes.X1 represents the hydrophilic polymer of polyethers-polyurethane copolymer type, its can be for example as " Hydrophilicrto polyether polyurethane " from Cardio Tech International, 78 E OlympiaAvenue, Woburn MA01801-2057, the U.S. obtains, and has 50% rate of water absorption and 60% swelling expansion rate.In order to prepare the solution of hydrophilic polymer X1, the hydrogel particle X1 of ormal weight is dissolved in ethanol-water mixture in stirring.Subsequently, the solution of hydrophilic polymer X1 is removed from fluid pipeline and shell channel (12), and via fluid pipeline and shell channel air amount, continued a few minutes.In this way that hydrogel layer is dry on the inwall of shell channel (12), thus the film of hydrophilic polymer on the inwall of shell channel (12), obtained according to coating processes of the present invention.

Claims (10)

1. for measuring at least one physics of liquid or the analytical system of chemical parameters, it comprises at least one physics for measuring liquid or at least one sensing element of chemical parameters, with for liquid being transported to sensing element and/or being transported away the fluid system of liquid from sensing element, it is characterized in that:
Described fluid system comprises at least one such fluid assembly, on the inner surface of this fluid assembly, have hydrophilic polymer film, the surface wettability for the aqueous solution that described hydrophilic polymer has is higher than the surface wettability there is no the fluid assembly inner surface under hydrophilic polymer film; The film of described hydrophilic polymer is also present in the inner surface of the liquid-conveyor zones of one or more sensing elements, and described inner surface directly contacts with analyzed liquid,
Wherein the film of hydrophilic polymer is according to following generation:
A) inner surface of fluid assembly is stood to physical chemistry pretreatment,
B) fluid assembly inner surface is contacted with hydrophilic polymer solution,
C) with the solution of the alternative hydrophilic polymer of gaseous medium, the inner surface of fluid assembly is kept by the solution-wet of the hydrophilic polymer of part, and
D) by hydrophilic polymer film being retained on the inner surface of fluid assembly except desolventizing.
2. the analytical system of claim 1, is characterized in that, analyzed liquid is physiological fluid.
3. the analytical system of claim 2, is characterized in that, described physiological fluid is blood, serum, blood plasma or urine.
4. any one analytical system of claim 1 to 3, is characterized in that, this analytical system comprises several sensing elements, to measure various physics and/or the chemical parameters of liquid.
5. the analytical system of claim 4, is characterized in that, described sensing element is the sensing element of sensing module form.
6. the analytical system of claim 5, is characterized in that, described fluid assembly is to be selected from following assembly: passage, pipe, valve, distributor, Connection Element or liquid receiving equipment.
7. the analytical system of claim 5, is characterized in that, the thickness of hydrophilic polymer film is between 0.01 to 50 micron.
8. the analytical system of claim 5, is characterized in that, the thickness of hydrophilic polymer film is between 0.01 to 10 micron.
9. the analytical system of claim 5, is characterized in that, the thickness of hydrophilic polymer film is between 0.01 to 5 micron.
10. the analytical system of claim 5, is characterized in that, described hydrophilic polymer is polyethers-polyurethane copolymer.
CN200510066910.0A 2004-04-26 2005-04-25 Method for surface hydrophilicity of fluid assembly and system Active CN1689711B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP04009817.0 2004-04-26
EP04009817 2004-04-26

Publications (2)

Publication Number Publication Date
CN1689711A CN1689711A (en) 2005-11-02
CN1689711B true CN1689711B (en) 2014-06-25

Family

ID=34924733

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200510066910.0A Active CN1689711B (en) 2004-04-26 2005-04-25 Method for surface hydrophilicity of fluid assembly and system

Country Status (9)

Country Link
US (1) US8394338B2 (en)
EP (1) EP1595605B1 (en)
JP (1) JP4878772B2 (en)
CN (1) CN1689711B (en)
AT (1) ATE466669T1 (en)
CA (2) CA2504944C (en)
DE (1) DE502005009508D1 (en)
DK (1) DK1595605T3 (en)
ES (1) ES2344457T3 (en)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1591778A1 (en) * 2004-04-26 2005-11-02 Roche Diagnostics GmbH Electrochemical gas sensor with hydrophilic membrane coating
JP2008286539A (en) * 2007-05-15 2008-11-27 Hitachi High-Technologies Corp Reaction cell for autoanalyzer, and method for surface finishing of the same
US20110008776A1 (en) * 2007-11-26 2011-01-13 Atonomics A/S Integrated separation and detection cartridge using magnetic particles with bimodal size distribution
EP2404867A1 (en) * 2010-07-09 2012-01-11 Trinean NV Method for preparing microfluidic devices
EP2409766A1 (en) 2010-07-23 2012-01-25 F. Hoffmann-La Roche AG Method for hydrophilising surfaces of fluid components and objects containing such components
AU2013267227B2 (en) 2012-05-31 2017-03-02 The University Of North Carolina At Chapel Hill Dissolution guided wetting of structured surfaces
US10767259B2 (en) 2013-07-19 2020-09-08 Agilent Technologies, Inc. Components with an atomic layer deposition coating and methods of producing the same
US20150024152A1 (en) 2013-07-19 2015-01-22 Agilent Technologies, Inc. Metal components with inert vapor phase coating on internal surfaces
JP6159644B2 (en) * 2013-10-29 2017-07-05 株式会社八光 Coating method for medical resin molding
CN107109644B (en) 2015-01-14 2020-11-06 安捷伦科技有限公司 Component with atomic layer deposition coating and method of making the same
RU2618845C1 (en) * 2015-12-03 2017-05-11 Общество с ограниченной ответственностью "Научно-исследовательский центр "Модифицированные полимеры" Method of manufacture of cuvette for analysis of liquid samples with hydrophilic interior surface
TWI675106B (en) * 2018-03-21 2019-10-21 緯創資通股份有限公司 Fluidic manipulation, modulefluidec detection system and test method by fluidic manipulation module
JP2023509773A (en) * 2020-01-13 2023-03-09 ベックマン コールター， インコーポレイテッド solid state ion selective electrode
CN113694873A (en) * 2021-09-14 2021-11-26 朱枫 Production and processing equipment and process of polyurethane waterproof coating

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3874850A (en) * 1972-07-24 1975-04-01 Radiometer As Blood analyzing method and apparatus
US4752426A (en) * 1985-06-27 1988-06-21 Yoshito Ikada Process for manufacture of plastic resinous tubes
EP0379156A2 (en) * 1989-01-17 1990-07-25 UNION CARBIDE CHEMICALS AND PLASTICS COMPANY INC. (a New York corporation) Improved hydrophilic lubricious coatings
US5212000A (en) * 1991-03-11 1993-05-18 The Dow Chemical Company Method for providing an inner-skinned functionalized coating on the lumen-defining surface of a hollow tube
US6447835B1 (en) * 2000-02-15 2002-09-10 Scimed Life Systems, Inc. Method of coating polymeric tubes used in medical devices

Family Cites Families (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4269685A (en) * 1979-10-16 1981-05-26 Mcneilabs, Inc. Disposable polarographic gas sensor system
IE51643B1 (en) * 1980-10-15 1987-01-21 Smith & Nephew Ass Coated articles and materials suitable for coating
US4835211A (en) * 1986-12-18 1989-05-30 The Procter & Gamble Company Cationic latex compositions capable of producing elastomers with hydrophilic surfaces
US4734445A (en) * 1986-12-18 1988-03-29 The Procter & Gamble Company Latex compositions capable of producing elastomers with hydrophilic surfaces
US4880883A (en) * 1987-06-03 1989-11-14 Wisconsin Alumni Research Foundation Biocompatible polyurethanes modified with lower alkyl sulfonate and lower alkyl carboxylate
US4885077A (en) * 1988-11-17 1989-12-05 Becton, Dickinson And Company Composite membrane, method for its preparation and electrolyte sensor including same
US5160790A (en) * 1990-11-01 1992-11-03 C. R. Bard, Inc. Lubricious hydrogel coatings
US5322063A (en) * 1991-10-04 1994-06-21 Eli Lilly And Company Hydrophilic polyurethane membranes for electrochemical glucose sensors
IL106922A (en) 1992-09-14 1998-08-16 Novartis Ag Composite materials with one or more wettable surfaces and process for their preparation
US5563233A (en) * 1994-11-16 1996-10-08 Tyndale Plains-Hunter, Ltd. Polyether polyurethane polymers and gels having improved absorption and slip properties
ATE297013T1 (en) 1995-11-08 2005-06-15 Hypoguard Ltd BIOSENSORS WITH MEMBRANE
US5932200A (en) * 1996-08-14 1999-08-03 Tyndale Plains-Hunter, Ltd. Polyether polyurethane polymers, gels, solutions and uses thereof
US6001067A (en) * 1997-03-04 1999-12-14 Shults; Mark C. Device and method for determining analyte levels
SE9702118D0 (en) * 1997-06-04 1997-06-04 Siemens Elema Ab Blood Analysis System
US5860676A (en) * 1997-06-13 1999-01-19 Swagelok Marketing Co. Modular block assembly using angled fasteners for interconnecting fluid components
KR100349000B1 (en) * 1998-07-09 2003-03-26 주식회사 아이센스 Manufacturing method of biosensor using hydrophilic polyurethane
KR100341565B1 (en) * 1998-11-11 2002-06-22 김윤 Fluorinated resins having a surface with high wettability
JP2000202907A (en) 1999-01-14 2000-07-25 Osaka Gas Co Ltd Lining tube and method for lining tube
JP2001163932A (en) * 1999-10-27 2001-06-19 Novartis Ag Method for modifying surface of material
ATE421685T1 (en) 1999-10-29 2009-02-15 Radiometer Medical Aps METHOD AND DEVICE FOR DETECTING A GAS BUBBLE IN A LIQUID
JP4282043B2 (en) 1999-12-06 2009-06-17 キヤノン株式会社 Recording liquid supply passage, recording liquid storage container, recording liquid supply apparatus including these, and surface modification method thereof
EP1130393A3 (en) * 2000-02-03 2001-11-28 Nihon Kohden Corporation Gas sensor and gas sensor system
WO2001096024A2 (en) * 2000-06-14 2001-12-20 Board Of Regents, The University Of Texas System Apparatus and method for fluid injection
TW513485B (en) * 2000-07-10 2002-12-11 Ind Tech Res Inst On-spot hydrophilic enhanced slide and preparation thereof
US6444324B1 (en) * 2000-12-01 2002-09-03 Scimed Life Systems, Inc. Lubricated catheter balloon
EP1373376B1 (en) 2001-03-08 2006-08-23 Bioartificial Gel Technologies Inc. Hydrogel attached to backing and method for making same
US7476533B2 (en) * 2002-04-19 2009-01-13 Adhesives Research, Inc. Diagnostic devices for use in the assaying of biological fluids
CA2757564C (en) * 2001-04-19 2013-01-08 Adhesives Research, Inc. Hydrophilic diagnostic devices for use in the assaying of biological fluids
US6756449B2 (en) 2002-02-27 2004-06-29 Medtronic, Inc. AnB block copolymers containing poly (vinyl pyrrolidone) units, medical devices, and methods
AU2003221808A1 (en) 2002-04-05 2003-10-27 Powerzyme, Inc. Analyte sensor
US6939450B2 (en) * 2002-10-08 2005-09-06 Abbott Laboratories Device having a flow channel
US20050054774A1 (en) * 2003-09-09 2005-03-10 Scimed Life Systems, Inc. Lubricious coating
US7544381B2 (en) * 2003-09-09 2009-06-09 Boston Scientific Scimed, Inc. Lubricious coatings for medical device
EP1591778A1 (en) * 2004-04-26 2005-11-02 Roche Diagnostics GmbH Electrochemical gas sensor with hydrophilic membrane coating

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3874850A (en) * 1972-07-24 1975-04-01 Radiometer As Blood analyzing method and apparatus
US4752426A (en) * 1985-06-27 1988-06-21 Yoshito Ikada Process for manufacture of plastic resinous tubes
EP0379156A2 (en) * 1989-01-17 1990-07-25 UNION CARBIDE CHEMICALS AND PLASTICS COMPANY INC. (a New York corporation) Improved hydrophilic lubricious coatings
US5212000A (en) * 1991-03-11 1993-05-18 The Dow Chemical Company Method for providing an inner-skinned functionalized coating on the lumen-defining surface of a hollow tube
US6447835B1 (en) * 2000-02-15 2002-09-10 Scimed Life Systems, Inc. Method of coating polymeric tubes used in medical devices

Also Published As

Publication number Publication date
ATE466669T1 (en) 2010-05-15
US20050255579A1 (en) 2005-11-17
DE502005009508D1 (en) 2010-06-17
EP1595605A1 (en) 2005-11-16
CN1689711A (en) 2005-11-02
CA2504944A1 (en) 2005-10-26
JP2005334872A (en) 2005-12-08
CA2504944C (en) 2010-01-12
JP4878772B2 (en) 2012-02-15
DK1595605T3 (en) 2010-08-16
ES2344457T3 (en) 2010-08-27
CA2655062C (en) 2013-02-05
US8394338B2 (en) 2013-03-12
EP1595605B1 (en) 2010-05-05
CA2655062A1 (en) 2005-10-26

Similar Documents

Publication Publication Date Title
CN1689711B (en) Method for surface hydrophilicity of fluid assembly and system
EP2060913B1 (en) Method for analysis of sample by capillary electrophoresis
KR100482285B1 (en) Fluid-type multiple electrochemical system and the preparation thereof
US8317168B2 (en) Mixer, mixing device and unit for measuring medical component
US7625760B2 (en) Analyzing cartridge and liquid feed control device
JP5060944B2 (en) Mixed electrode
CN100496749C (en) Spotting device and method for high concentration spot deposition on microarrays and other mini devices
US20090148348A1 (en) Plastic surfaces and apparatuses for reduced adsorption of solutes and methods of preparing the same
WO1999003584A1 (en) Microfluidic analyzer module
FR2591747A1 (en) ENZYMATIC OR ION SELECTIVE ELECTRODE ANALYZER AND METHOD OF USE
GB2222681A (en) Enzymatic electrode and electrode module and method of use
JP2008064701A (en) A device for rotational analysis, measurement method, and testing method
JP2021504704A (en) Microfluidic device
GB2620692A (en) Compound distribution in microfluidic devices
JP4546889B2 (en) Chip with weighing unit
JP3643863B2 (en) Liquid holder and manufacturing method thereof
KR20190008344A (en) Test system for analyzing samples of body fluids
JP6956719B2 (en) Goods for collecting fluids
US9623440B2 (en) Method for hydrophilizing surfaces of fluidic components and parts containing such components
JP2004132955A (en) Analytical test cartridge and method
CN110785220A (en) Modified filter membrane and use thereof
US9945773B2 (en) Flow cell and liquid feed system
CN110573256B (en) Sample processing system and method
JP2006145450A (en) Optical analytical device
US20220097044A1 (en) Diagnostic Device with Integrated Sampler and Holder

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant